Sulfurized dyes and process of making same.



Hammer: HEIMANN, or DESSAU,

GERMANY, ASSIGNOR TO ACTIEN GESELLSCHAFT FT QlR ANILIN FABRIKATION, OFBERLIN, GERMANY.

SULFURIZEID DYES AND PROCESS OF MAKING SAME.

1 $05,515. No Drawing.

To all "whom it may concern:

Be it known that I, Hmxiucu l-IEIMANN, a citizen of the German Empire,residing at Dessau, Germany. my post-olfice address beingFriedrich-Solmeiderstrasse (i3, Dessau, Germany, have invented new anduseful lii'iprovenients in new Sulfurized Dyes and Processes of MakingSame, of which the following is a specification.

in a co-pending application, serially numbered 726,121, I describe andclaim generally new sulfurized dyes fast to washing and to chlorin whichcan be obtained by acting with a sulfurizing agent upon a4-hydroxydiarylamin in which only the i-hydroxyaryl group is capable of,assuming the paraquinoid form. Now in my present invention I claim aspecial class of these new dyes which derive from those of sucht-hydroxydiarylamins in which the ore aryl residue is a phenyl group andthe other aryl residue is a naphthyl group and in which one of the twoc-positions contains a hydroxyl group, or from their derivativescontaining in the benzene or in the naphthalene nucleus fur thersuitable nnivalent substitnents, such as a halogen, an alkyl or alkoxygroup, a carboxylic group, etc., the sul'fonic group being excepted.

In producing the new sulfur dyes according to this invention I can alsouse as parent material the corresponding thio compounds, 1'. 0., thecorresponding derivatives of a thiophenylnaphthylamin, thus for instanceinstead of l-hydroxyphenyl-l-naphthylamin I may employ the4-hydroxy-thiophenyl-1- naphthylamin,

The parent materials of my present invlcntion therefore possess thefollowing nuc ens:

Specification of Letters Patent. Application filed October 16, 1912.Serial No. 726,124.

Patented J uly 28, 191-1.

together; the mixture is then heated to about 220-240 C. during abouti:8 hours; thus a dye is obtained which produces on cotton without auiordant in a bath containing an alkali sulfid dull blue tints which arevery fast to washing and show a very remarkable 't'astness to chlorin.

(3.) 50 parts oi. -l--hydroxypl1cnyl-1 -naphthylainin are melted with 50parts of snl Fur, the temperature being then gradually raised to 200"This temperature is maintained for about 8 hours; the temperature isthen raised to about 210-250 C. and maintained at this point for about-l hours. The product of this operation dyes cotton without a mordantintense bluegray tints of good tastness to washing and remarkablet'astness to chlorin. If in the foregoing example, the temperature israiscd only to 300 C. a dye is obtained which produces tints that aremore violet-gray but also show a rcmm'kablc fastness to chlorin.

(3.) 40 parts of sulfur and 50 parts of i hydroxyphenylQ-naphthylaminare melted together and the mass then heated to about. 2204 10 (1.during about =l---8 hours. The dye thus obtained produces on unmordantcdcotton from a dye-bath containing an alkali sultld violet-black shadeswhich possess an excellent fastuess to washing and which are fast tochlorin.

(4.) 28 parts of l-hydroxy-El-carboxyphenyl-2-naphthylamin, 10 parts ofsoda-lye 43 136., 100 parts of crystallized sodium sulfid and 80 partsof sulfur are heated to the boil, using a reflux condenser, in an oilbath during about 20-40 hours. The dye thus produced may be isolated inthe known manner; it produces on cotton with the aid of alkalipolysulfids a black tint fast to washing.

The new dyes derived from a -i-hydroxyphenylnaphthylamin and obtained asabove are in the dry state when pulverized, generally speaking, blackpowders, practically insoluble in alcohol, glacial acetic acid, benzene,nitrobenzene and chloro-benzene; they are soluble in anilin and pyridin,generally speaking, to a violet solution and they dissolve inconcentrated sulfuric acid, generally speaking, to a green to bluesolution an( in 25% fuming sulfuric acid, generally speaking, to blue toviolet solutions which solutions are gradually decolorized on theaddition of aluminium powder.

is ohidous to those skilled in the art that my present invention is notlimited to the foregoing examples or to the details given therein. Thusfor instance instead of the parent materials above used -hydrorq or thelike may be sulfurized according to my present invention It may also hestated that the proportions of the ingredients as well as the temperature of reaction or the duration of heating may be al'tu'cd within widelimits without departing from the scope. of my present in- \ention.

l laving new described my invention and the manner in which it may beperformed, what I claim is-- 1. The manufacture of new sulfurized dyesfast to washing and to chlorln by acting with a sulfuriraing: agent uponthose l;-hydrox \'diarylainins in which one aryl r iidue is a phenylgroup and the other aryl residue is a naphthyl' group and in which onethe two i -positions contains a hydroxyl ioup, which parent materialscontain no sulfonic group and possess the following nucleus:

in which diagram the figures (4) represent the two -il-positionsreferred to.

3. The manufacture of new sulfurized dyes fast to washing and to chlorinby acting; with sulfur in the presence of'a substance being a liquid atthe temperatures in question upon those ldiydroxydiarylamins iuwhich onearyl residue is a phenyl group in which diagram the figures (4i)represent the two 4pos1t1ons referred to.

The manufacture of new sulfurised dyes fast to washing and to chlorin byset ing; with a sulfurizing agent upon t-hydroXyphenyl-l-napl'ithylamin.

5, The manufacture of a new sulfu ized dye fast to washing and tochlorin by acting with sulfur upon d-hydroxyphenyl1- naphthylainin. I

6. as new articles of manufacture new sulit'urized dyes fast to washingto chlorin derived from a l-hydroxydiarylainin in which the one 'arylresidue is a phenyl group and the other aryl residue is a naphthyl groupand in which one of the two 4l-positions contains a hydrony group, whi.1i parent materials contain no sulfonic group and possess the followingnucleus:

in which diagram the figures (at) represent the two l-positions referredto, which new dyes are practically insoluble in alcohol, glacial aceticacid, benzene, nitrobenzene and chlorobenzene, and which new dyes aresoluble in anilin and pyridin and dissolve in concentrated sulfuric acidand in 25% fuming sulfuric acid to intensely colored ire solutions, andwhich new dye-s produce on UIiDIOIClZUIlZBCl cotton from dye-bathcontaining an alkali sulfid, generally speaking, blue to black tintsfast to Washing and to chlorin, and which new dyes are also capable ofbeing dyed from a hydrosulfite vat, yield-- ing, generally speaking, ayellow vat, from which cotton is dyed blue to black tints.

7. As new articles of manufacture new sulfurized dyes derived from athydrcxyphenylnaphthylamin, not containing a sul fo nic group, which newdyes in the dry state when pulverized, generally speaking, are blackpowders, which new dyes are pros-- tically insoluble in alcohol, glacialacetic acid, benzene, nitrobenzene and chlorobenzone, and which new dyesare soluble in anilin, andfpyridin, generally speaking, to

a violet solution, and these new d es dissolving in concentratedsulfuric aci generally spealn'ng, to a green to blue solution, whichremains unaltered on the addition of boric acid but is graduallydecolorized by the addition of aluminium powder, and which new dyesdissolve in fuming sulfuric acid, generally speaking, to blue to violetsolutions which solutions remain unaltered on the addition of boric acidbut are gradually decolorized by the addition of aluminium powder, andwhich new dyes produce on unmordanted cotton from a dyebath containingan alkali sulfid, generally speaking, blue to black tints fast towashing and to chlorin, and which new dyes are also capable of beingdyed from a hydrosulfite vat, yielding a yellow vat, from which cottonis dyed blue to black tints.

8. As a new article of manufacture a new sulfurized dye which may beobtained by acting with sulfur upon 4t-hydroxyphen 1- l-naphthylamin,which new dye in the ry state when pulverized is a black powder which ispractically insoluble in alcohol, glacial acetic acid, benzene,nitrobenzene and chlorobenzcnc. and which new dye is soluble in anilinand pyridin to a violet solution, this new dye dissolving inconcentrated sulfuric acid to a green-blue solution which 'remainsunaltered on the addition of boric acid but is gradually decolorized bythe addition of aluminium powder, and which new dye dissolves in 25%fuming sulfuric acid to a violet-blue solution which solution remainsunaltered on the addition ol boric acid but is gradually decolorized bythe addition of aluminium powder, and which new dye produces from adye-bath containing an alkali sulfid a dull blue tint fast to washingand to chlorin, this new dye being also capable of dyeing from ahydrosulfite vat yielding a yellow vat, from which cotton is dyed a dullblue tint.

'In testimony whereof I have signed my name to this specification in thepresence of two subscribing witnesses.

' HEINRICH-l I-IEIMANN.

Witnesses RUDOLPH. FRICKE, Doms Knann.

Benton 0! this patent may be obtained for live cents each, by addressingthe Commissioner or I'atcntm Wnnhdnzton, D. C."

